Phase diagrams of YBa2Cu4O8 and YBa2Cu3.5O7.5 in the pressure range 1 bar≤PO2≤3000 bar

The P-T-x phase diagram of the pseudobinary system (Y-Ba-Cu-O)-O₂ has been further investigated in the oxygen pressure range between 1 and 3000 bar. The stability ranges of the phases YBa₂Cu₄O₈ (124), YBa₂Cu_3.5O_7.5−x (123.5) and YBa₂Cu₃O_7−x (123) have been determined. Long duration experiments showed that the 123 phase is not stable at least down to 7 bar≤P≤20 bar oxygen and 900°C. It is not clear whether at lower pressures and temperatures the 123 phase is thermodynamically stable or metastable due to low reaction rates. In the presence of excess CuO, the 124 is the stable phase. The melting of 124 pellets at P_O2=2800 bar shows that even at this pressure the 124 compound melts incongruently. Using the phase diagram data we could change the T_c of 123.5 from 16 to 70 K by varying systematically the nonstoichiometry. Due to a narrow homogeneity range the T_c of 124 remained constant but is different for powder pellets (81 K) and for crystals (70 K), probably due to the influence of the flux. Single crystals of both 124 and 123.5 with dimensions up to 4 mm were grown from the flux under high oxygen pressure.     

SUPERCONDUCTING PROPERTIES AND STRUCTURAL PERFECTION OF EPITAXIAL YBa2Cu3O7-x THIN FILMS

High quality epitaxial YBa₂Cu₃O_7-x thin films have been succcessfully prepared by dc magnetron sputtering deposition, on (100) and (110) aligned SrTiO₃, LaAlO₃ and yttria-stabilized zirconia (YSZ) substrates. The films showed zero resistance around 90 K and had a J_c (at 77 K, H=0) over 10⁶A/cm². It was found that superconducting properties and structures of the films were strongly dependent on oxygen pressure and substrate temperature. The epitaxial structure of the films have been studied by X-ray diffraction. Rutherford backscattering and channeling spectroscopy, X-ray double-crystal diffraction and transmission election microscopy. The experimental results demonstrated that the epitaxial YBa₂Cu₃O_7-x films had excellent superconducting properties and quite perfect structure.     

The nuclear contribution to the specific heat of single crystals of YBa2Cu3O7 and Bi2Sr2CaCu2O8

Specific heat data below 1 K of Bi₂Sr₂CaCu₂O₈ and YBa₂Cu₃O₇ are analyzed. For YBa₂Cu₃O₇ the nuclear specific heat, C_N, amounts to 38T⁻² μJ/mol K. C_N for Bi₂Sr₂CaCu₂O₈ exceeds that of YBa₂Cu₃O₇ by a factor of 15. The nuclear quadrupolar specific heat contribution alone is insufficient to explain the data for YBa₂Cu₃O₇, while lack of NQR data does not allow such a comparison in Bi₂Sr₂CaCu₂O₈ to be made. The contribution to C_N from nuclear spins coupled via the contact hyperfine interaction with correlated magnetic spins (in the CuO₂ plane) is derived as a function of the correlation length. This contribution can be treated independently from the quadrupolar term. We show that the excess specific heat in YBa₂Cu₃O₇ likely originates in a few percentage of an impurity (oxygen deficient) phase with a strong hyperfine field on the Cu nuclei.     

Studies of synthesizing behaviors and superconductivity of sol-gel YBaCuO samples in flowing oxygen atmosphere

Systematic studies of synthesizing behaviors of sol-gel YBa₂Cu₃O_7-x samples in flowing oxygen atmosphere and their superconductivity have been performed. A set of high temperature ?-T curves has been obtained for the whole synthesizing process. After four rounds of synthesizing, the resistivity of the sample was around ? = 1.00 × 10^-3 ?cm at room temperature. The ?-T curve of the fourth round shows that the orthorhombic to tetragonal phase transformation of the sample occurs around 600°C, which is lower than that of the YBa₂Cu₃O_7-x sample prepared by conventional solid-state reaction method. Other measurements, such as X-ray diffraction, SEM measurement and low temperature R-T and M-T measurement, were also performed. And the R-T and M-T measurement results suggest that during the synthesizing process, there exist some state at which the sample has better superconductivity than the other states. Moreover, we found screw dislocations presenting on the sample broken surface from the SEM images. This will change the concept that the screw dislocations can only grow on the surface of the YBCO thin films and single crystals.     

Formation of Ca-doped YBa2Cu4O8 phase in thin films

Ca-doped YBa₂Cu₄O₈ (124) thin films are prepared on (100) SrTiO₃ substrates by annealing the amorphous films deposited using a pulsed laser deposition technique. The X-ray diffraction measurements show that the Ca-doped YBa₂Cu₄O₈ phase is formed by annealing below 800°C at a oxygen pressure of 1 atm. The 124 films have c-axis orientation normal to the substrates. As the Ca content increases, the proportion of the 123 impurity phase in the samples increases. The onset temperature of superconductivity of the Y(Ca)Ba₂Cu₄O₈ films increases from 79 K to 88 K with an increase Ca-substitution for 5 to 10% of Y.     

DETERMINATION OF THE OXYGEN CONTENT IN YBa2Cu3O7-y FILMS

A method for determination of the oxygen content (y) in YBa₂Cu₃O_7-y films has been established, in which the lattice conetant difference (b-a) of the films was measured and used to fit the function of (b-a) vs y for the experimental data of bulk YBaaCuaO?-y given in the literature. It is suggested that the function of (b-a) vs y can indeed be used in the case of film. In this process the twin structure of the YBa₂Cu₃O_7-y films was used.     

Phase equilibria at low oxygen partial pressure in the Y---Ba---Cu---O system

The phase equilibria around YBa₂Cu₃O_7−x (123) and YBa₂Cu₄O₈ (124) phases at low oxygen partial pressure (1 atm) were investigated by X-ray diffraction and thermal analysis. The coexistence of 123 and 124 phase was confirmed under 1 atm oxygen pressure. By using the high temperature X-ray diffraction method, the univariant reaction YBa₂Cu₃O_7−x+Cu₂OY₂BaCu₂O₂+O₂ was identified. The oxygen partial pressure dependence of several univariant reactions has been investigated and the existence of two invariant reactions of L+O₂YBa₂Cu₃O_7−x+ BaCuO₂+CuO+Cu₂O and L+Y₂BaCuO₅+O₂YBa₂Cu₃O_7−x+CuO+Cu₂O was deduced to occur at 1103 K under 0.0032 atm O₂ and at 1143 K under 0.0085 atm O₂, respectively.     

EFFECTS OF THE QUALITY OF SUBSTRATE ON THE STRUCTURE AND SUPERCONDUCTING PROPERTIES OF Yba2Cu3O7-x THIN FILM

We have systematically investigated the structures, morphologies, microwave surface resistance, DC performances and the substrate qualities of three YBa₂Cu₃O_7-x(YBCO) thin films 30mm in diameter. The three samples deposited by the same process have been proved of different properties. It has been shown that the structure and superconducting properties of the thin film depend strongly on the quality of substrate.     

Realization and properties of ramp-type YBa2Cu3O7−δ/Au/Nb junctions

All-thin-film ramp type Josephson junctions between YBa₂Cu₃O_7−δ and Nb have been fabricated. This procedure allows connections between high-T_c and low-T_c superconductors at different crystal sides of the high-T_c superconductor on one chip, which is of great interest for novel phase devices. A thin Au layer is incorporated as a chemical barrier to avoid oxygen transfer from the YBa₂Cu₃O_7−δ to the Nb. Critical current densities up to 600 A/cm² are obtained at T=4.2 K, with typical R_nA values of 0.8 μΩ cm². The variation of the magnetic field dependence of the critical current with the angle between the junction barrier and the YBa₂Cu₃O_7−δ crystal axes is explained by considering a predominant d_x²−y² order parameter symmetry of the YBa₂Cu₃O_7−δ. The successful fabrication of these junctions allows the implementation of novel superconducting electronics, such as complementary Josephson circuitry or proposed qubit concepts, using the unconventional order parameter symmetry of the high-T_c superconductor.     

Hole distribution and madelung energy in the high-Tc oxide superconductors

Evidence is presented that in high-T_c superconductors the electrostatic interaction as expressed by the Madelung energy is the key factor in determining the charge distribution and in particular the distribution of the holes between the CuO₂-planes and other structural subunits. Specifically, this explains the phase diagram (T_c as a function of oxygen content and oxidizing power) of cation-substituted YBa₂Cu₃O_6+y and the oxygen ordering in YBa₂Cu₃O_6.5. Moreover, we argue that the dependence of T_c on strontium content in La_2−xSr_xCuO₄ is similarly due to the fact that holes go into the (La,Sr)O-sheets as well as into the CuO₂-planes.     

Effect of lead addition to Bi-based 2222 superconducting cuprates Bi2-xPbxSr2(Y, Ce)2Cu2O10+δ

Bi_2-xPb_xSr₂(Y, Ce)₂Cu₂O_10+δ, a new family of lead containing Bi-2222 compounds has been synthesized and effects of annealing in high pressure of oxygen studied. Lead-free Bi₂Sr₂(Y, Ce)₂Cu₂O_10+δ synthesized under flowing oxygen is known to be non-superconducting, but annealing under high oxygen pressure (100 bar) at 500°C, induced superconductivity with T_c=25 K. On substitution of lead (x>0.4), the superconductivity appears even in samples synthesized under flowing oxygen (1 bar). T_c increases with oxygen annealing pressure for all compositions, and it also increases with Pb content at a given oxygen pressure. These findings are discussed.     

YBa2Cu3-xFexOy的离子配位与结构转变

本文用穆斯堡尔效应、X射线衍射等手段,系统研究了掺铁的YBa₂Cu_3-xFe_xO_y(0.01≤x≤0.2)超导氧化物经过不同温度真空退火后超导转变温度T_c、相结构、氧含量与氧配位之间的关系,结果表明,铁主要占Cu(1)位,铁含量的增加和高温真空退火都引起正交相向四方相转变,T_c逐渐减小至零,但这两种转变过程的铁的配位结构和氧含量却不相同,对前者,相变是与出现相当数量的六配位F 关键词：     

THE SCREENING EFFECT OF PHONON MODES IN HIGH-Tc OXIDE SUPERCONDUCTOR

This paper presents three different kinds of infrared (IR) spectra of oxide materials. The first one is the IR reflection spectra of Ti₂Ba₂Ca₂Cu₃O₁₀ superconducting film at the incident angles 7°, 12° and 30°. The second one is the IR spectra of nonsuperconducting ceramic materials YBa₂Cu₃O₆ and PrBa₂Cu₃O₇. The third one is the IR spectra of superconductor YBa₂Cu₃O_7-δ and of its film with the c-axis perpendicular to the film plane, as well as the changes in the spectra of these materials after annealing at different temperatures. It is found that in the spectra of high-T_c oxide superconductor, only the phonon modes along c-axis can be observed while the modes in a-b plane are absent. But in the spectra of nonsuperconductors the modes in a-b plane can be observed, particularly in the absorption spectra of the semiconductor YBa₂Cu₃O₆, all eleven allowed IR active modes have been detected. We suggest that the above experimental phenomena may result from the fact that the phonon modes vibrating in the a-b plane of the high-T_c oxide superconducting materials are almost screened by the free carriers which can move only in a-b plane.     

Critical current density of polycrystalline YBa2Cu3O7−δ consisting of tin-coated grains

Tin and its oxides have been introduced into the intergrain areas of polycrystalline YBa₂Cu₃O_7−δ by coating the crystalline grains with a thin layer of tin and sintering the ceramics in flowing oxygen and argon. The transport critical current density J_c at 77 K in a magnetic field of 0−1.5 T is enhanced as a result of the coating. A probable improvement of the intergrain weak links is suggested.     

Transient creep of YBa2Cu3O7−x superconductor

Rapid changes of oxygen partial pressure (P_O2) between 10³ and 2.1×10⁴ Pa have been carried out during steady-state plastic deformation of polycrystalline YBa₂Cu₃O_7−x (YBCO) at temperatures between 825 and 900°C. Transient creep was observed after such P_O2 changes. The analysis of these creep transients allowed the determination of the chemical diffusion coefficient for reequilibration, which is identical to that found from thermogravimetry and electrical conductivity experiments for oxygen vacancies.     

Electron concentration in YBa2Cu3O6.9 single crystals determined from field electron emission spectroscopic measurements

Results of field electron emission spectroscopic investigations of YBa₂Cu₃O_6.9 single crystal specimens oriented perpendicular to the c-axis are presented. It is shown that the shift of the total energy distribution of field-emitted electrons from YBa₂Cu₃O_6.9 along the energy scale with increasing electric-field strength at the surface of the specimen is due to the penetration of the electric field into the subsurface region of the YBa₂Cu₃O_6.9 specimen. The electron concentration in YBa₂Cu₃O_6.9 found from spectroscopic measurements is n=(2−4) × 10²¹ cm⁻³. Field electron emission spectroscopy and microscopy of YBa₂Cu₃O_6.9 allows one to draw the conclusion that the electron concentration in the bulk of the material does not change with cooling of specimens from 300 K to 115 K.     

Aspects of annealing and free surface crystallization of YBCO thin films

We describe a method of high temperature annealing in which the control of oxygen partial pressure is the principal experimental determinant in obtaining highly c oriented thin films of YBa₂Cu₃O_{7 − δ} on YSZ. Film crystallization, morphology and substrate interactions are discussed with detailed reference to the equilibria existing in the YBCO system. A model based on the melt-assisted crystallization of the precursor tetragonal compound, beginning at the free film surface, is used to explain the observed c texturing. Excellent Josephson coupling between grains of YBa₂Cu₃O_{7 − δ} in our films is related to melt-assisted growth. We discuss the adverse effects of annealing in pure oxygen at high temperatures.     

Intercalation thermodynamics and chemical diffusion of oxygen in the solid solution YBa2Cu3−xCoxO6+δ

The equilibrium oxygen content as a function of the temperature and oxygen pressure was measured for the solid solution YBa₂Cu_3−xCo_xO_6+δ, where x=0, 0.2, 0.4, 0.6, 0.8, by using coulometric titration in the temperature range 600–850°C and oxygen pressures between 10⁻⁵ and 1.0 atm. The change in the partial molar enthalpy and entropy of the intercalated oxygen was determined at different oxygen and cobalt contents. The oxygen chemical diffusion was studied by thermogravimetric relaxation in the oxygen-controlled atmosphere. The thermodynamic data were employed to determine how the chemical diffusion coefficient, the thermodynamic factor and the random-diffusion coefficient depend on oxygen content in specimens with different cobalt concentration. The oxygen intercalation thermodynamics and diffusivity results provide evidence of ordering phenomena on a microscopic scale in the basal plane of the tetragonal solid solution YBa₂Cu_3−xCo_xO_6+δ. A model for the oxygen diffusion is suggested to explain the large difference between the random and tracer diffusion coefficients in YBa₂Cu₃O_6+δ     

Dependence of the laser-induced voltages on the oxygen content in normal state YBa2Cu3O7−δ films

Our investigation on the relation between oxygen content and the laser-induced voltages of the YBa₂Cu₃O_7−δ films in normal-state shows that deoxygenation of the superconducting films reduces the laser-induced voltages greatly, even reverses the sign of the signals at large oxygen deficiency. The absolute value of the negative signal at large oxygen deficiency can be greater than that of the positive signal.     

Temperature dependence of the critical current in YBa2Cu3O7−δ and Bi2Sr2Ca1Cu2O8 Josephson junctions

We have studied the stationary Josephson effect on YBa₂Cu₃O_7−δ (T_c=90 K) and Bi₂Sr₂Ca₁Cu₂ O₈ (T_c=80 K and 87 K for two samples of different origin) ceramic based junctions. The temperature dependence of the critical current near T_c has been found as I_c≈(T_c-T) for the Y-Ba-Cu-O samples indicating that they should be classified as S-N-I-N-S type junctions. The I-V curves of the Bi-Sr-Ca-Cu samples show the typical behaviour of S-I-S structures. Using Ambegaokar-Baratoff's theory for Bi₂Sr₂Ca₁Cu₂O₈, the temperature dependence of the superconducting state gap Δ(T) was calculated and it was evaluated that 1.452Δ(0)/k_BT_c3.5.